EP1600520A1 - Acier à résistant aux températures élevées - Google Patents

Acier à résistant aux températures élevées Download PDF

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Publication number
EP1600520A1
EP1600520A1 EP05445031A EP05445031A EP1600520A1 EP 1600520 A1 EP1600520 A1 EP 1600520A1 EP 05445031 A EP05445031 A EP 05445031A EP 05445031 A EP05445031 A EP 05445031A EP 1600520 A1 EP1600520 A1 EP 1600520A1
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EP
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Prior art keywords
zero
stainless steel
steel
alloy
hours
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German (de)
English (en)
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EP1600520B1 (fr
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Mikael Schuisky
Andreas Rosberg
Kenneth S. Göransson
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure relates generally to a steel product, which at high temperatures forms an oxide scale with good surface conductivity and an excellent adhesion to the underlying steel.
  • it relates to a ferritic chromium steel suitable for the use as interconnects or bipolar plates in solid oxide fuel cells or other high temperature applications such as catalytic converters in cars and trucks.
  • Ferritic chromium steels are used for applications with high requirements on heat resistance, such as for example interconnect materials in S olid O xide F uel C ells (SOFC) or if alloyed with Al, as a material for catalytic converters. They are very suitable materials for use in SOFC applications since the T hermal E xpansion C oefficients (TEC) of ferritic steels are close to the TECs of the electro-active ceramic materials used in the SOFC stack, such as yttrium-stabilized zirconia (YSZ) which is the common material used as electrolyte in the fuel cell. This has, for instance, been studied by Linderoth et al. in "Investigation of Fe-Cr ferritic steels as SOFC interconnect material", Mat. Res. Soc. Symp. Proc., Vol. 575, (1999), pp. 325-330.
  • TEC T hermal E xpansion C oefficients
  • the oxide scale formed on the steel interconnect material does not spall off or crack due to thermal cycling, i.e., the oxide scale should have good adhesion.
  • the formed oxide scale should also have good electrical conductivity and not grow too thick during the life time of the fuel cell, since thicker oxide scales will lead to an increased electrical resistance.
  • the formed oxide should also be chemically resistant to the gases used as fuels in an SOFC, i.e., no volatile metal-containing species such as chromium oxyhydroxides should be formed. Volatile species such as chromium oxyhydroxide will contaminate the electro-active ceramic materials in a SOFC stack, which will lead to a decrease in the efficiency of the fuel cell.
  • ferritic chromium steel are usually alloyed with aluminum and/or silicon, which form Al 2 O 3 and/or SiO 2 at the working temperature of the SOFC. Both these oxides are good electrical insulating oxides, which will increase the electrical resistance of the cell and lower the fuel cell efficiency.
  • the new developed steels are alloyed with group III elements, i.e., Sc, La and Y and/or other rare earth elements (REM).
  • group III elements i.e., Sc, La and Y and/or other rare earth elements (REM).
  • the addition of La, Y or REM is made to increase the lifetime of the material at high temperatures.
  • Strong oxide formers such as La, Y and REM are said to decreases the oxygen ion mobility in the formed Cr 2 O 3 scale, which will lead to a decrease in the growth rate of the oxide scale.
  • the amount of added REM to the steel has to be carefully monitored, since too high a concentration of REM will lead to production process difficulties, as well as undesired corrosion properties of the steel.
  • the steel is alloyed with a small amount of La (0.01 - 0.4% by weight) and optionally also with small amounts of Y and Ce (0.1 to 0.4% by weight).
  • the steel is also alloyed with either Y ( ⁇ 0.5% by weight) or REM ( ⁇ 0.2% by weight) or La (0.005 - 0.1 % by weight).
  • ferritic steel for interconnects in SOFC.
  • Two of these are the steel sorts A and B (see further details of A and B in Example 3 below), A being alloyed with 0.04% La, and B with a La content of max 0.2% by weight.
  • All the above mentioned patents and commercially available steels are alloyed with small amounts of rare earth metals such as Y, La and Ce. The addition of reactive rare earth metals will lead to a decrease in corrosion resistance compared with the steel alloy of this invention.
  • said alloy is heat resistant at temperatures up to 900°C and that the oxide scale formed does not grow too thick. Therefore, the mass gain per unit area of said alloy is less than 1.5 mg/cm 2 , when the steel alloy has been oxidized in air or in air + 1 % H 2 O mixture for 1000 hours at 850°C or any environment similar to the gases used in a Solid Oxide Fuel Cell.
  • the grown oxide scale does not spall off, i.e., has a good adhesion to the underlying alloy.
  • the thermal expansion of said alloy should not deviate considerably from the thermal expansions of the anode material or the electrolyte material used in the fuel cell. Therefore, said alloy has a thermal expansion coefficient of 10 to 15 ⁇ 10 -6 °C -1 in the temperature range 0 to 900°C, or even more preferably 11 to 14 ⁇ 10 -6 °C -1 , and most preferably 11.5 to 13 ⁇ 10 -6 °C -1 .
  • the thermal expansion mismatch (TEM) between the electro-active ceramic materials in the fuel cell and the thermal expansion of said alloy is not greater than ⁇ 25%, or preferably less than ⁇ 20%, or most preferred lower than ⁇ 15%.
  • thermal expansion mismatch is defined as (TEC ss - TEC ce )/TEC ss , where the TEC ss is the thermal expansion of the steel alloy and TEC ce is the thermal expansion of the electro-active ceramic materials used in anode-supported fuel cells.
  • the bipolar plate works as a current collector in a fuel cell.
  • the contact resistance of the steel alloy is kept as low as possible throughout the lifetime of the fuel cell.
  • the area specific resistance (ASR) of said alloy in a SOFC setup should be kept low but also the increment of ASR with time is kept as low as possible. If the increment of the ASR is large, this can lead to a decrease of the fuel cell efficiency.
  • Chemical Composition The chemical composition of the steel alloy consists essentially of (by weight-%):
  • the chemical composition comprises the following elements (by weight-%):
  • the grown oxide scale does not spall off, i.e., has a good adhesion to the underlying alloy.
  • Thermal Expansion To be able to use steel as interconnects or bipolar plates in SOFC, the thermal expansion of the alloy should not deviate greatly from the thermal expansion of the anode material or the electrolyte material used in the fuel cell. Therefore, the steel alloy has a thermal expansion coefficient of 10 to 15 ⁇ 10 -6 °C -1 in the temperature range 0 to 900°C, or even more preferably 11 to 14 ⁇ 10 -6 °C -1 , and most preferably 11.5 to 13 ⁇ 10 -6 °C -1 . Further, the thermal expansion mismatch (TEM) between the electro-active ceramic materials in the fuel cell and the thermal expansion of said alloy is not greater than ⁇ 25%, preferably less than ⁇ 20%, and most preferably lower than ⁇ 15%.
  • TEM thermal expansion mismatch
  • thermal expansion mismatch is defined as (TEC ss -TEC ce )/TEC ss , where the TEC ss is the thermal expansion of the alloy and TEC ce is the thermal expansion of the electro-active ceramic materials.
  • the thermal expansion of said steel alloy can be tuned to match the thermal expansion of the electro-active ceramic materials in the fuel cell by carefully monitoring the amount of alloying elements, such as nickel, in the steel alloy.
  • Conductivity The disclosed steel alloy has a good conductivity and, in a SOFC setup, have an ASR of less than 50 m ⁇ cm 2 after 1000 hours, preferably an ASR even lower that 25 m ⁇ cm 2 after 1000 hours, on both anode and cathode side of the interconnect.
  • the increment of the ASR is not greater than 10 m ⁇ cm 2 per 1000 hours, preferably even lower than 5 m ⁇ cm 2 per 1000 hours on both the anode and the cathode side of the interconnect. This factor promotes a good efficiency of the fuel cell throughout the life time of the fuel cell, which might be as long as 40 000 hours.
  • the steel alloy is produced by ordinary metallurgical steel making routines to the chemical composition as described, for example, in the following Examples. Then said steel alloy is hot-rolled down to an intermediate size, and thereafter cold-rolled in several steps with a number of recrystallization steps, until a final specific thickness of normally less than 3 mm, and a width of maximally 400 mm.
  • the linear thermal expansion of said steel alloy was determined by dilatometer measurement and was found to be 12.3 ⁇ 10 -6 °C -1 for the temperature range 30 to 900°C.
  • Example 1 A 0.2 mm thick steel alloy strip with a nominal composition (by weight) of max 0.2 % C, max 0.1 % N, max 0.1 % O, max 0.4 % Si, max 0.5 % Al, max 0.5 % Mn, 20 to 25 % Cr, max 2.0 % Ni, 0,001 to 0.1 % Zr + Hf, max 0.5 % Ti, max 2.5 % Mo +W, max 0.5 % V, max 1.25 % Nb +Ta and balance of Fe (with naturally occurring impurities) was produced by an ordinary steel making process, followed by hot-rolling down to a thickness of less than 4 mm.
  • Coupons of the five steel alloy strips with the size 70 x 30 x 0.2 mm were oxidized in air at 850°C for 336, 672 and 1008 hours, respectively.
  • the mass gain per unit area is plotted as a function of time for the five steel alloys. According to Figure 1, a mass gain of less than 1.1 mg/cm 2 per 1000 hours is obtained for the steel alloy of Example 1, insuring a good high temperature corrosion resistance and a lower growth rate of the formed oxide scale.
  • FIG 2 a cross sectional Scanning Electron Microscopy (SEM) micrograph of the formed oxide scale after 336 hours at 850°C in air on the steel alloy of Example 1 is shown.
  • SEM Scanning Electron Microscopy
  • the chemical composition of the formed oxide scale after oxidization in air for 336 hours at 850°C was determined by Glow Discharge Optical Emission Spectroscopy (GDOES).
  • GDOES Glow Discharge Optical Emission Spectroscopy
  • the GDOES depth profile for the formed oxide scale is shown.
  • the different scales for different elements should be noted.
  • the manganese content in the formed oxide scale increases at the surface to about 12% by weight.
  • the thickness of this manganese-rich oxide scale is about 0.5 ⁇ m, followed by a more chromium-rich oxide scale of approximately less than 2.4 ⁇ m.
  • a manganese-rich oxide scale at an outermost layer at the surface is of importance since ternary chromium oxides such as MnCr 2 O 3 are believed to lower the formation of volatile chromium species such as chromium oxyhyroxides. It can also be seen that the titanium content is approximately 0.4% by weight in the oxide scale. Finally, it can be noted that at the interface of the steel alloy and the oxide scale, a region of silicon oxide is obtained. The formation of silicon oxide should be kept as low as possible but is unavoidable if the steel is alloyed or has small residuals of silicon in the matrix.
  • Example 2 As an additional example of an exemplary embodiment of the disclosed steel alloy, coupons of the final steel alloy strip with the sizes of approximately 30 x 40 x 0.057 mm were oxidized in air at both 750°C and 850°C for 500 and 1000 hours, respectively. In Table 3, a summary of oxidization results of the four samples together with the exact coupon sizes of the initial samples is given.
  • the result at 750°C showed a very low mass gain per unit area, lower than 0.2 mg/cm 2 after 500 hours of oxidization and the mass gain did not increase greatly after 1000 hours. Instead, it was still lower than 0.3 mg/cm 2 after 1000 hours.
  • the mass gain per unit area was larger but still low, less than 1.1 mg/cm 2 , which was also the result for the thicker strip (0.2 mm) samples, oxidized in Example 1.
  • Example 3 As a third example, coupons of exemplary embodiments of the disclosed steel alloy and the four test melts (Sandvik ID numbers 433, 434, 436 and 437) described in Example 1 and the Sandvik 0C44 alloy, were oxidized together with coupons of two commercially available steel grades designed for the use as interconnects in SOFC, alloy A and alloy B at 850°C in air + 1 % H 2 O for 500 hours.
  • Figure 4 the weight gain for the different steel grades after oxidation at 850°C in air + 1% H 2 O is shown.
  • the exemplary embodiments of the disclosed steel alloy have a much lower weight gain compared with the four Sandvik test melts, and also have a much lower weight gain than the two commercially available steel grades.
  • a low weight gain is equal to a good high temperature corrosion resistance.
  • the second lowest weight gain is obtained by the Sandvik 0C44 alloy with the nominal composition (by weight) of max 0.018% C, max 0.025% N, max 0.5% Si, max 0.35% Mn, 21.1 to 21.8% Cr, max 0.3% Ni, max 0.02% P, max 0.007% S, max 0.15% Mo, max 0.010% Ti, max 0.01 % Nb, max 0.03 % Ce, max 0.015% Mg and balance of Fe (with naturally occurring impurities).
  • the steel alloy Sandvik ID number 434 with a high Mn content has the largest weight gain almost 3 mg/cm 2 after 500 hours of exposure.
  • Example 4 All the three previous examples have described the excellent high temperature corrosion resistance of exemplary embodiments of disclosed steel alloy. In this fourth example, the low electrical resistivity of the exemplary steel alloys will be exemplified.
  • the contact resistance was measured in dry air for 2900 hours at 750°C with a temperature peak of 850°C for 10 hours in the beginning.
  • the load of the contact was 1 kg/cm 2 at the start and the contact area was 0.5 cm 2 .
  • the measured area specific resistance (ASR) was initially, i.e., after the 850°C temperature peak lower than 15 m ⁇ cm 2 and had after 2900 hours, including 6 thermal cycles, increased to below 25 m ⁇ cm 2 .
  • the increment of the ASR with time was lower than 5 m ⁇ cm 2 per 1000 hours. If extrapolated linearly, the ASR of the contact would be less than 200 m ⁇ cm 2 after 40,000 hours of exposure. It is important for the fuel cell efficiency that the ASR is low throughout the lifetime of the fuel cell.
  • the ASR was even lower, well under 10 m ⁇ cm 2 after 600 hours of exposure.
  • the increment of the ASR was very low, under 2 m ⁇ cm 2 per 1000 hours. If extrapolated linearly the ASR of the contact on the anode side would be much lower than 200 m ⁇ cm 2 after 40,000 hours of exposure, even lower than 100 m ⁇ cm 2 after 40,000 hours of exposure.

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EP05445031A 2004-05-19 2005-05-17 Acier résistant aux températures élevées Expired - Lifetime EP1600520B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0401292A SE527933C2 (sv) 2004-05-19 2004-05-19 Värmebeständigt stål
SE0401292 2004-05-19

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EP1600520A1 true EP1600520A1 (fr) 2005-11-30
EP1600520B1 EP1600520B1 (fr) 2011-10-12

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US (1) US20050265885A1 (fr)
EP (1) EP1600520B1 (fr)
JP (1) JP2007538157A (fr)
KR (1) KR20070012495A (fr)
CN (1) CN100545293C (fr)
AT (1) ATE528417T1 (fr)
AU (1) AU2005243292B2 (fr)
CA (1) CA2566144A1 (fr)
DK (1) DK1600520T3 (fr)
ES (1) ES2374821T3 (fr)
SE (1) SE527933C2 (fr)
WO (1) WO2005111254A1 (fr)

Cited By (3)

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EP1882756A1 (fr) * 2006-07-26 2008-01-30 Sandvik Intellectual Property AB Acier ferritique à haute teneur en chrome
US20120171464A1 (en) * 2006-07-07 2012-07-05 Plansee Se Porous support substrate with an electrically conductive ceramic layer
WO2021009100A1 (fr) * 2019-07-17 2021-01-21 Haldor Topsøe A/S Procédé d'enrichissement en chrome d'interconnexions en acier ferritique pour des applications d'empilement de piles à oxyde solide

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CN1993849A (zh) * 2004-06-25 2007-07-04 通用汽车公司 不锈钢合金和双极板
JP4794843B2 (ja) * 2004-10-06 2011-10-19 東京瓦斯株式会社 耐熱合金製インターコネクタを有する固体酸化物形燃料電池の運転方法
CA2659596C (fr) * 2006-07-26 2015-04-28 Sandvik Intellectual Property Ab Acier au chrome ferritique
CN103078121A (zh) * 2012-12-07 2013-05-01 上海锦众信息科技有限公司 一种燃料电池用铬氮复合极板材料的制备方法
CN103972576A (zh) * 2014-04-03 2014-08-06 上海华篷防爆科技有限公司 一种含有聚合物电解质膜的固态氢发电装置
CN103972546B (zh) * 2014-04-03 2016-09-14 上海华篷防爆科技有限公司 带有不锈钢储氢瓶的发电装置
CN106663822B (zh) * 2014-11-06 2020-03-03 京瓷株式会社 导电构件、蓄电池组装置、模块、模块收纳装置以及导电构件的制造方法
JP6967894B2 (ja) * 2016-07-05 2021-11-17 大阪瓦斯株式会社 セル間接続部材の製造方法
CN109355591A (zh) * 2018-11-19 2019-02-19 深圳市致远动力科技有限公司 一种耐高温合金
CN110938782A (zh) * 2019-10-30 2020-03-31 武汉科技大学 一种低成本耐热钢及其制备方法

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WO2021009100A1 (fr) * 2019-07-17 2021-01-21 Haldor Topsøe A/S Procédé d'enrichissement en chrome d'interconnexions en acier ferritique pour des applications d'empilement de piles à oxyde solide
CN114127339A (zh) * 2019-07-17 2022-03-01 托普索公司 对用于固体氧化物电池堆应用的铁素体钢互连件进行铬升级的方法
US12286721B2 (en) 2019-07-17 2025-04-29 Haldor Topsøe A/S Method for chromium upgrading of ferritic steel interconnects for solid oxide cell stack applications

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CA2566144A1 (fr) 2005-11-24
AU2005243292B2 (en) 2010-04-08
CN100545293C (zh) 2009-09-30
ATE528417T1 (de) 2011-10-15
KR20070012495A (ko) 2007-01-25
WO2005111254A1 (fr) 2005-11-24
DK1600520T3 (da) 2012-01-23
SE0401292L (sv) 2005-11-20
US20050265885A1 (en) 2005-12-01
JP2007538157A (ja) 2007-12-27
AU2005243292A1 (en) 2005-11-24
SE0401292D0 (sv) 2004-05-19
SE527933C2 (sv) 2006-07-11
CN1957102A (zh) 2007-05-02
ES2374821T3 (es) 2012-02-22

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